2327. Citrinin

Nomenclature

CAS number: 518-75-2
(3R,4S)-4,6-Dihydro-8-hydroxy-3,4,5-trimethyl-6-oxo-3H-2-benzopyran-7-carboxylic acid; Antimycin.
C13H14O5; mol wt 250.25.
C 62.39%, H 5.64%, O 31.97%.

Description and references

Antibiotic substance produced by a white spore aspergillus which has been placed under the species name Aspergillus niveus (Thorn and Raper). Also produced in small quantities by Penicillium citrinum: Hetherington, Raistrick, Trans. R. Soc. London B220, 269 (1931); Raistrick, Smith, Chem. Ind. (London) 60, 828 (1941); Timonin, Science 96, 494 (1942); Timonin, Rovatt, Can. J. Public Health 35, 80 (1944). Identity with antimycin: Haese, Arch. Pharm. 296, 227 (1963). Structure: Brown et al., J. Chem. Soc. 1949, 867; Warren et al., J. Am. Chem. Soc. 79, 3812 (1957); Kovac et al., Nature 190, 1104 (1961). Synthesis: Cartwright et al., J. Chem. Soc. 1949, 1563; J. A. Barber et al., J. Chem. Soc. Perkin Trans. 1 1986, 2101. Stereochemistry: Cram, J. Am. Chem. Soc. 72, 1001 (1950); Mehta, Whalley, J. Chem. Soc. 1963, 3777; Mathieson, Whalley, ibid. 1964, 4640. Physical characteristics and toxicity: Nagai et al., Chem. Zentralbl. 1958, 8088, C.A. 55, 1914 (1961). Crystal and molecular structure: Rodig, Chem. Commun. 1971, 1553. Biosynthesis: J. Barber et al., J. Chem. Soc. Perkin Trans. 1 1981, 2577; L. Colombo et al., ibid. 2594. Physicochemical data: A. E. Pohland et al., Pure Appl. Chem. 54, 2219 (1982). Toxicology: A. M. Ambrose, F. De Eds, J. Pharmacol. Exp. Ther. 88, 173 (1946). Review: Saito et al., “Yellowed Rice Toxins” in Microbial Toxins vol. VI, A. Ciegler, S. Kadis, A. Ajl, Eds. (Academic Press, New York, 1971) pp 357-367.

Chemical structure

Properties

Lemon-yellow needles from alcohol, dec 175°. [α]D18 -37.4° (c = 1.15 in alc.). uv max: 250, 331 nm (E1%1cm 370, 418). Strong acid. Practically insol in water. Sol in alcohol, dioxane, dilute alkali. Solns change color with changes in pH, from lemon-yellow at pH 4.6 to cherry-red at pH 9.9. Poisonous. LD50 in mice, rats (mg/kg): 35, 67 i.p. (Ambrose, De Eds).

Derivative

Methyl citrinin.
C14H16O5; mol wt 264.27.
C 63.63%, H 6.10%, O 30.27%.

Properties

Plates from benzene, dec 139°. [α]D18 +217.1° (c = 0.38 in acetone). uv max: 260, 334 nm (E1%1cm 520, 151.6). Sol in hot alcohol; moderately sol in chloroform. Practically insol in petr ether.

Derivative

Dihydrocitrinin.
C13H16O5; mol wt 252.26.
C 61.90%, H 6.39%, O 31.71%.

Properties

Prisms from benzene, dec 171°. [α]D18 -18.8° (c = 4.148 in chloroform). uv max: 260, 330 nm (E1%1cm 400, 100). Sol in alcohol, acetone, chloroform; sparingly sol in benzene, petr ether.